4,4′-Thiodianiline (TDA) is the organosulfur compound with the formula (H2NC6H4)2S. It is classified as a diamine and a thioether. It typically appears as an (off-)white solid powder. An analogue of TDA is the drug dapsone, for which the sulphur species is oxidised.

4,4′-Thioaniline
Names
Preferred IUPAC name
4,4′-Sulfanediyldianiline
Other names
p,p′-Thiodianiline; Bis(4-aminophenyl) sulfide; 4,4′-Thioaniline; 4-(4-Aminophenyl)sulfanylaniline
Identifiers
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.004.883 Edit this at Wikidata
EC Number
  • 205-370-9
KEGG
UNII
  • InChI=1S/C12H12N2S/c13-9-1-5-11(6-2-9)15-12-7-3-10(14)4-8-12/h1-8H,13-14H2 ☒N
    Key: ICNFHJVPAJKPHW-UHFFFAOYSA-N ☒N
  • C1=CC(=CC=C1N)SC2=CC=C(C=C2)N
Properties
C12H12N2S
Molar mass 216.3 g/mol
Appearance Brown-brown violet powder or needles
Density 1.26 g/cm3
Melting point 105 to 107 °C (221 to 225 °F; 378 to 380 K)
Boiling point 464.8 °C (868.6 °F; 738.0 K) @ 760mmHg
Hazards
Flash point 234.9 °C (454.8 °F; 508.0 K)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Synthesis

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Sulfur is boiled in excess aniline over several hours to produce three isomers (1,1′; 1,4; 4,4′) of TDA.[1] The same journal documents syntheses of similar and overlapping compounds by Merz and Weith in 1871, and K. A. Hoffman in 1894. A study by Nietzki and Bothof[2] shows indications that including an oxide of lead may maximize the yield of the 4,4′ variant that this page refers to.

Uses

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TDA was used as a chemical intermediate in the production of three dyes: CI mordant yellow 16, milling red G and milling red FR, as well as the medicine Dapsone. TDA has also been used in the synthesis of polyimine vitrimers.[3]

Production

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TDA is no longer produced in the USA.

Toxicity

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TDA has caused mutations in some strains of Salmonella typhimurium and has caused tumors in laboratory mice and rats.

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References

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  1. ^ Hodgson, Herbert Henry (January 1924). "Direct sulphuration of aniline". J. Chem. Soc., Trans. 1924 (125): 1855–1858. doi:10.1039/CT9242501855. Retrieved 11 February 2016.
  2. ^ Nietzki, R; Bothof, Heinrich (1894). "The Understanding of Thioanilines". Reports of the German Chemical Society. 27 (3): 3261–3263. doi:10.1002/cber.189402703119.
  3. ^ Schoustra, Sybren K.; Dijksman, Joshua A.; Zuilhof, Han; Smulders, Maarten M. J. (2021). "Molecular control over vitrimer-like mechanics – tuneable dynamic motifs based on the Hammett equation in polyimine materials". Chemical Science. 12 (1): 293–302. doi:10.1039/d0sc05458e. ISSN 2041-6520. PMC 8178953. PMID 34163597.